Widespread mud volcanism across the thick (〈= 14 km) seismically active sedimentary prism of the Gulf of Cadiz is driven by tectonic activity along extensive strike-slip faults and thrusts associated with the accommodation of the Africa-Eurasia convergence and building of the Arc of Gibraltar, respectively. An investigation of eleven active sites located on the Moroccan Margin and in deeper waters across the wedge showed that light volatile hydrocarbon gases vented at the mud volcanoes (MVs) have distinct, mainly thermogenic, origins. Gases of higher and lower thermal maturities are mixed at Ginsburg and Mercator MVs on the Moroccan Margin, probably because high maturity gases that are trapped beneath evaporite deposits are transported upwards at the MVs and mixed with shallower, less mature, thermogenic gases during migration. At all other sites except for the westernmost Porto MV, delta C-13-CH4 and delta H-2-CH4 values of similar to -50 parts per thousand and -200 parts per thousand, respectively, suggest a common origin for methane; however, the ratio of CH4/(C2H6 + C3H8) varies from similar to 10 to > 7000 between sites. Mixing of shallow biogenic and deep thermogenic gases cannot account for the observed compositions which instead result mainly from extensive migration of thermogenic gases in the deeply-buried sediments, possibly associated with biodegradation of C2+ homologues and secondary methane production at Captain Arutyunov and Carlos Ribeiro MVs. At the deep-water Bonjardim, Olenin and Carlos Ribeiro MVs, generation of C2+-enriched gases is probably promoted by high heat flux anomalies which have been measured in the western area of the wedge. At Porto MV, gases are highly enriched in CH4 having delta C-13-CH4 similar to -50 parts per thousand, as at most sites, but markedly lower delta H-2-CH4 Values 〈 -250 parts per thousand, suggesting that it is not generated by thermal cracking of n-alkanes but rather that it has a deep Archaeal origin. The presence of petroleum-type hydrocarbons is consistent with a thermogenic origin, and at sites where CH4 is predominant support the suggestion that gases have experienced extensive transport during which they mobilized oil from sediments similar to 2-4 km deep. These fluids then migrate into shallower, thermally immature muds, driving their mobilization and extrusion at the seafloor. At Porto MV, the limited presence of petroleum in mud breccia sediments further supports the hypothesis of a predominantly deep microbial origin of CH4. (C) 2009 Elsevier B.V. All rights reserved.